Hydrogenated products



Patented Feb. 15, 1938' UNITED STATES PATENT OFFICE HYDROGENATED PRODUCTS Norman D.. Scott and JosephFrederic Walker, Niagara Falls, N. Y., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a

corporation of Delaware No Drawing. Original application October 20, 1933, Serial No. 694,516. Divided. and this application July 25, 1934, Serial No. 736,960 g 11 Claims.

This invention relates to the manufacture of hydrogenated products made from naphthalene or the homologs of naphthalene and particularly to the manufacture of dihydro naphthalene and its. homologs and polymers of these dihydro compounds. This application is a division of our copending application Ser. No. 694,516 filedv Oct. 20, 1933.

The reduction of naphthalene by sodium and alcohol has long been known. Although it is stated in the literature that the reduction can be controlled to give dihyclronaphthalene rather than tetralin by working at moderate temperatures, the process has never attained practical importance. Presumably this is largely due .to its inefficiency and the tendency to waste hydrogen. ,In connection withhis work on lithium naphthalene reactions, the separation of dihydronaphthalene' was reported by Schlenk (An nalen 463, p. 91). He decomposed with alcohol 7 the addition Compound of lithium and naphthalene which had been prepared in ethyl ether as solvent with a fieaction time of eight days. Both the slowness of this process andthe expense of lithium make this method impractical; Schlenk 'reports that in experiments of shorter duration for the reaction of lithium with naphthalene he obtained after alcoholysis an equimolar mixture of naphthalene and dihydronaphthalene.

An object of this invention is to provide an improved. method for the preparation or. dihydronaphthalene and its homologs with eflicient utilization both of alkali metal and of the hydrocarbon being reduced. A further object is to provide means of completing the reaction in a short time. A further object is to control the this reaction between the ,dihydro compound; and the alkali metal compound is profoundly in-,

iluenced by relatively small temperature changes.

At low temperatures, the reaction is greatly in hibited; or, if the temperature is sufficiently low, it is substantially completely prevented. For example, the reaction'between dihydronaphthalene and disodium naphthalene occurs readily at-temperatures of C. and higher, but as the temperature is decreased .below 25 C., the reaction is progressively inhibited and at temperatures around C. the reaction is not appreciable within a reasonable length of'time. In the case of the homologs of dihydronaphthalene, for example, dihydro alpha methylnaphthalene or dihydro beta methylnaphthalene, the same temperature influence maybeobserved although the critical temperature may vary somewhat.

By proper application of these discoveries, in accordance with our invention, we are able to prepare dihydronaphthalene or its homologs in higher yields than heretofore has been possible in experiments of reasonable duration. Furthermanner that the reaction produces small amounts of the dihydro compound, most of the hydrocarbon being converted to a useful resinous material which apparently is a polymer of the dlhydro v compound. 5

One possible reason for the low yield of dihydronaphthalene obtained by prior methods is based upon the fact that ordinarily not more than one gram atom of alkali metal will react withone gram molecule of naphthalene in reasonable time, e. g., several hours. This proportion of reacted metal is equivalent to the forma: 'tion of one mole of 'dimetal naphthalene, leaving one mole of naphthalene unreacted. When the reaction mixture is hydrolyzed, the resulting hydrolysis product .theoreti'cally is an equlmolecular mixture of naphthalene and dihydronaphthalene. As explained more fully below, by means of our invention, we are able to. convert 90%"or more of. naphthalene or a naphthalene I l'iomolog to the corresponding dihydro compound in a single operation. The product can be analyzed by titrating with solutions of bromine in chloroform at 0 C. Each molecule of dihydronaphthalene absorbs one molecule of bromine without literation of 1-131.

In preparing the dihydro compounds of naphthalene and its homologs and the polymers of the dihydro compounds, we use sodium in preference to otheralkali metals mainly because of its cheapness and availability. By way of illustration', our invention will be described with refer ence to the use of sodium as the alkali metal component of the reactions involved. I In order to obtain a sodium-naphthalene compound within a reasonable length of time, it is necessary to adopt special methods. A satisfac tory method for reacting sodium with naphtha", lens and similar. hydrocarbons is described and 15 more, we are able to modify the process in'such claimed in the co-pending applications of Norman D. Scott, Ser. No. 638,524, filed October 19, 1932; Serial No. 678,261, filed June 29, 1933; and

Serial No. 691,574, filed September 29, 1933. Briefly stated this method comprises reacting the hydrocarbons with sodium in a solvent me: dium comprising substantial amounts of certain active ethers. The ethers which are used for this purpose are'substantially inert to sodium and to the sodium hydrocarbon compound which is formed in the reaction and may be divided into two classes as follows:

1. Dialkyl mono-ethers having a CHaO group and in which the atomic ratio of oxygen to carbon is not less than 1:4. Examples in this group are dimethyl ether and methylethyl ether.

2. Poly-ethers, that is, ethers having more than one ether oxygen linkage, for example the fully alkylated derivatives of ethylene glycol or glycerol.

-' These ethers may be used as solvent medium either alone or mixed with other inert solvents such as parafiln hydrocarbons,- aromatic 'hydrojcarbons or inert ethers which do not fall within Preparation of dihydronaphthalene In accordance with our invention, dihydronaphthalene is prepared by first reacting naphthalene with an alkali metal, for example sodium, to form a sodium naphthalene addition product and subsequently hydrolyzing the sodium naphe thalene compound; while taking measures to inhibit the above mentioned reaction of sodium naphthalene with the dihydronaphthalene which is formed by the hydrolysis. In accordance with our invention, two methods may be used to in-.

hibit the reaction between the dihydronaphthalene and the sodium naphthalene compound, namely, by .(a) carrying out the hydrolysis ata temperature at which the reaction between the sodium compound and the dihydronaphthalene is inhibited, that is, at atemperature below 25 C., preferably at a temperature around -30 C.;

and (b) by hydrolyzing the sodium compound substantially as fast as itis formed and in such manner that no substantial amounts of sodium compound is allowed to accumulate in' the reaction mixture. The second method may be car- -ried out at temperatures in which the sodiuin compound and the idihydronaphthalene readily react, for example 25 to 30 C. E

In one method of practicing our invention. naphthalene is dissolved in a suitable ether solvent, that is one of the active" ethers described above, for example the dimethyl ether of ethylene glycol, in a vessel equipped with amechanical stirrer and provided with means for maintaining an atmosphere ofinitrogen or other inert gas in the reaction vessel. Approximately "2 gram at'omaofj sodium for each gram molecule of naphthalene in the solution is placed in a perforated container which is suspended in the solution.

During the resulting reaction between the sodium and the naphthalene, the reaction vessel is cooled by means of a cooling bath which may consist of a hydrocarbon such as kerosene to which is added solidified carbon dioxide as required to maintain the desired temperature. The reaction mixture is constantly stirred and the temperature therein is maintained at 20 to -30 C. As the reaction Proceeds, the solution takes on a green color due to the formation of the sodium naphthalene compound. At any time, after the green color has formed, a hydrolyzing agent, for example water, is added either continuously or intermittently with continuous stirring and cooling so that the reaction temperature: does not rise above 20 C. The hydrolysis reaction is exothermic; hence the rate of addition of water must be so adjusted as to prevent undue rise in temperature. If sufliclent water is first added to the reaction mixture, the green color may disappear, due to the conversion of the sodium naphthalene compound to dihydronaphthalene. However, in a short time the solution will be again colored green, indicating that as the sodium naphthalene compound is hydrolyzed, the remainingnaphthalene continues to react with the sodium. As the reaction between the naphthalene and sodium proceeds, the hydrolyzing agent is added in small amounts continuously or from time to time until substantially all the sodium has'reacted. Preferably, a

slight excess of the hydrolyzing agent is added.

The sodium hydroxide formed by the hydrolysis,

' being insoluble in the solvent ether, forms a precipitate. .The solution is filtered to remove the sodium hydroxide and the, filtrate is distilled to separate. the dihydronaphthalene from the reaction mixture. Preferably, the hydrolyzed solution' is saturated with carbon dioxide prior to filtration to convert the sodium hydroxide to bicarbonate", which generally is easier to filter out than sodium hydroxidei; If the filtrate is distilled at atmospheric pressure, the dihydronaphthalene distills over at 205 to 210 C. Ifdesired, the dihydronaphthalene fraction maybe further puri-v fied or separated into its isomers by known means.

In another method of preparing dihydronaphthalene by our invention, naphthalene is dissolved in a suitable active ether having a boiling point above room temperature, for example,

the dimethyl ether of ethylene glycol, and reacted with sodium at room temperature under an atmosphere of nitrogen. As soon as the reaction between the sodium and the naphthalene has commenced as indicated by the formation of a green color around the sodium, the hydrolyzing agent, preferably water, is slowly added to the solution, either continuously or intermittently. As the reaction proceeds, care is taken that the rate of addition of water is suflicient to prevent the spread of the green color throughout the solution but is not great enough to prevent the formation of green color on the surface of the sodium or in close proximity thereto.- Preferably,

I the addition of water-is carried out in such manner that the sodium particles are covered with a film of the green sodium naphthalene'compound but the reaction mixture is substantially free from the green compound. If the water is added too rapidly it is likely to react with the sodium which will ,be indicated by the formation of a coating of white sodium oxide on the sodium particles The dihydronaphthalene is recovered from the reaction mixture by the method described above. i I

The .dihydronaphthalene made according to e which is chiefly 1, 4-dihydronaphthalene; it melts 2,1'oa21a our invention appears to be an isomeric mixture at a temperature between and C. and has Preparation of dihydronaphthalene polymer Dihydronaphthalene polymer may be prepared according to our invention by reacting dihydronaphthalene with the above described green sodium naphthalene compound.

In order that this reaction may proceed within a reasonable length of time, the temperature of the reaction mixture should be -not lower than about 20 C. and preferably not higherthan around C. At the higher temperatures, that is, above 30 C., the polymer may be prepared but polymerized,

the degree of polymerization. is ordinarily somewhat lowered and the product tends to be colored. If the polymerization occurs at temperatures between 25 and 30 C. good yields of a highly substantially colorless, resinous polymer having a melting point around 100 C. may be obtained. At temperatures much below 20 Ci, the reaction between',dihydronaphthalene and the, sodium compound is slow and the yield is low. However, fair yieldsof the polymer may be obtained at temperatures'as low as 15 C. The reaction may be carried out by first preparing substantially pure dihydronaphthalene and adding this to the green sodium naphthalene compound dissolved in one of the aforementioned active ethers or the polymerization maybe eifected by hydrolyzing a mixture of. naphthalene andsodium naphthalene produced by reacting sodium with naphthalene in a suitable active ether solvent. I f

By way of illustration, one method of preparing a dihydronaphthalene polymer of high molecular weight according to our invention will be that the green color of the sodium naphthalene compound is never discharged. When the reaction is complete, the reaction mixture is, filtered to remove the precipitated sodium hydroxide and the filtrate is distilled to remove solvent and re- 'acted by-products, leaving the dihydronaphthalene polymer as the distillation residue. Pref erably, we first distill at atmospheric pressure to remove the solvent etherand then distill in vacuum at a pressure of 1v to 8 -millimetersof. v.mercury until the distillation. of volatile material is completed; On cooling, the liquid residue f.solidifies to a slightly fluorescent, resinous material which melts in the neighborhood of 100 C ss has been carried out without untemperature, the solid resinous esubstantlally colorless. Slightly If the pr I impure samples. of this material usually have a light yellow color.

In the above described method of preparing \the dihydronaphthalene polymer, more or less of a dimer of dihydronaphthalene is formed which is removed during the final distillation. The resulting product, when this dimer is prac- 'tically completely removed, has a molecular weight of-400 or higher and a melting point of about 97-103 C. If desired, the purification step may be modified so as to allow all or part of. the

dimer formed to remain in the final product, thus resulting in a product having a lower molecular, weight anda lower. melting point. We prefer, however, to remove all or the greater part of the dimer in order to produce the high molecular weight product which has useful resinous properties. The high molecular weight product has a refractive index of approximately 1.60 and a density of about 1.0.

The above mentioned dimer of dihydronaphthalene which is produced in the distillation step,

' is obtained in its crude state 'as a viscous liquid, distilling over at 200 to 230 C. at a pressure of 1 to 3 mm. of mercury. ,This is probably the dimer, contaminated with some dihydronaph-' 0 C. At room temperature it is a viscous liquid, v

' which is practically colorless with a slight blue fluorescence when pure; slightly impure samples ordinarily have a light yellow color. The solu bilities of the dimer resemble those of the higher polymers of dihydronaphthalene as described below, i. e. it is soluble in hydrocarbons, chlorinated hydrocarbons, ketones and esters but is in- I soluble in water or alcohols. Both the dimer and the solid polymer are decomposed when heated to 350 to 400 C. A small amount of the dimer is sometimes formed in the herein described preparation of dihydronaphthalene. The corresponding-dim'ers of naphthalene homologs may be made by our method; these have properties similar tothose of the dihydronaphthalene dimer. I

The dimer of. dihydronaphthalene has a boiling poiritof about 200 'C. under a'pressure of one millimeter and has a refractive index of about 1.6 at'24-C. m"

If desired, the dimer of dihydronaphthalene may be further polymerized to the resinous polymers having molecular weights of 400' or higher by reacting the dimer with the sodium naphthalene compound under the same conditions that are required for the reaction with dihydronaphthalene and subsequently hydrolyzing.

' chlorinated hydrocarbons, for example carbon tetrachloride, in aliphatic ketones, for example acetone, in fatty acid esters, for example ethyl acetate, and in the various ethers, includingthose; which are suitable for making disodium naphthalene-as described above, and in turpen tine. It is insoluble in water and in alcohols and may be precipitated from its solutions by the addition of these substances. We have discovered that acenaphthene reacts with sodium like the naphthalene homologs. Thatis, acenaphthene, dissolved in one of the aforementioned active" ethers will react with sodium to form a sodium compound which may be hydrolyzed in accordance with our herein described'invention to produce dlhydro acenaphthene; its liquid dimer and its higher, solid polymers. The sodium compound of acenaphthene reacts with dihydro acenaphthene or its dimer in the same manner that sodium naphthalene re- J acts with dihydronaphthalene or its dimer.

In'preparing solid polymers by our methods, complex products may be made by utilizing two or more different hydrocarbons. For example,

sodium naphthalene may be reacted with dihydro acenaphthene. This method of practicing our invention may be accomplished either by starting with a mixture of hydrocarbons, e. g., a mixture of naphthalene and acenaphthene, or the respective sodium compound and dihydro compound may be prepared separately and then reacted.

Example 1 A quantity of sodium was finely divided by agitating at a temperature above its melting point in xylene. The xylene was washed from the pulverized sodium by means of dimethyl ether and 15 grams of the sodium was placed in a reaction vessel with 200 cc. of liquid dimethylether. Thirty-two grams ofnaphthalene were added to the reaction vessel and the materials were allowed to react under an atmosphere of dry, oxygen-free nitrogen for a period of one hour at, the boiling point of the dimethyl ether, that is, at about 24 C. During the reaction, a

green color was formed indicating the formation of thesodium naphthalene compound. After the reaction was complete, an excess of methanol 'was slowly added with agitation to completely decolorize the reaction mixture, while the temdimethyl ether then was evaporated oil and the residue was dissolved in diethyl ether. The di- 'Boiling Fraction me I Total yiel Fractions. land 2 were mainly dihydronaph- -thalene; 1,2-dihydronaphthalene melts at 8 C.

and the 1,4-i s omer melts at 25 C.

' Example 2 3 Naphthalene (256 grams) dissolved in- 1.5 liters of dimethyl glycol ether was reacted with one gramatom of sodium per mole of naphthalene 75 underv an atmosphere offnitrogen at room tem-- perature was maintained at about -24 C. The

Percent yield about 100 C.

perature. When the reaction was complete, the

resulting green solution of sodium naphthalene was very slowly added to a quantity of dimethylglycol ether which contained a little water. During the addition of the green solution water was slowly added to the dimethyl glycol ether and the additions of the green solution and water'were made at such rates that thegreen color of the sodium naphthalene solution was discarged substantially instantaneously upon its introduction into the moist solvent. After filtration to remove the sodium hydroxide formed, the solvent was evaporated off and the residue i'ractionally distilled under vacuum. The product obtained was a substantially equimolecular mixture of naphthaleneand dihydronaphthalene, corresponding to 84% of the naphthalene originally taken.

\ 7 Example 3 Naphthalene was reacted with sodium under an atmosphere of nitrogen in a solution of di methyl glycol ether at a temperature of 30 C.

As soon as the green color of the sodium compound was formed, methanol was slowly added at a rate insufllcient to completely discharge the green color. After a period of about one hour,

the green color disappeared. At this point, the

solution was filter. to remove precipitated sodium methylate an the residue was fractionated to separate the reactionproduct. Of the naphthalene used, about 85% was recovered as a mixture of approximately equal parts by weight of naphthalene and dlhydronaphthalene. No polymer or other non-volatile compounds were formed. V

Example 4 One mole of naphthalene was reacted under an atmosphere of-nitrogen with two moles of sodium in dimethyl glycol ether at 20-50 C. As soon as the reaction started, small amounts'of water were continuously added at such rates that the formation of a green color in the solution was prevented, but the reaction of the sodium with the naphthalene was not substantially inhibited. By this method, 77% of the original naphthalene.

was converted into dlhydronaphthalene.

-Ezample 5:

One mole of naphthalene was-reacted under .an atmosphere of nitrogen with one gram atom of sodium in diethyl glycol ether at room temperature. After the reaction was complete, sufficient water was added to decolorize the solution and the resulting mixture wasfiltered to remove precipitated sodium hydroxide. 'The filtrate was then reacted under an atmosphere 01' nitrogen with a further gram atom of sodium of 1 to 3 millimeters until substantially all volatile materials'were distilled over, The residue which was equivalent to 85% of the naphthalene originally taken, was a substantially colorless,'

transparent,- slightly fluorescent solid, melting at 10 An equimolecular mixture of naphthalene and dihydronaphthalene (575 grams) was-dissolved in 500 c. c. of .dimethyl glycol ether-and reacted with 44 grams of sodium under'an atmosphere i5 dimer having a molecular weightof about 264 water then was added to decolorize thesolutiom Onfractionation, 290 grams of a practically colorless polymer, similar to the product of Example 5, was obtained. The other products separated from the reaction mixture by the fractionation were 63 grams of the dimer of dihydronaphthalene, a viscous liquid which boils, at.

around 200 C. at 1 mm. of mercury pressure, 123

grams of dihydronaphthalene and 64' grams of naphthalene. l

Example 7 About ten' grams of the dimer of dihydronaphthalene described in Example 6 was reacted under an atmosphere of nitrogen at room temperature with 10 cc. of a green solution made by reacting sodium with naphthalene in dimethyl glycol ether. The total naphthalene equivalent contained in .-.this green solution, both as free naphthalene and as sodium naphthalene, was 1.5 grams. The dimer and the green solution were mixed with about cc. of dimethyl glycol ether under an atmosphere of..nitrogen and reacted at 26-28 C. After decolorization with water and filtration to remove sodium hydroxide, the solvent ether was H distilled off and the remaining liquid was distilled at 1 2 millimeters of mercury pressure until substantially all the volatile inaterials had beendistilled oil, which required a maximum distillation temperature of about 205 C. On cooling, the

glycol ether.

slowly added at such rate that the formation of a residue solidified to a hard transparent resin,

; similar to the product of Example 6. This resin was found to have a molecular weight of about 419.

Example 8 Forty-eightgrams of alpha-methylnaphthalene was reacted in 500 cc. of dimethyl glycol ether with 6 grams of sodium with an'atmosphere of nitrogen at room temperature. As the reaction proceeded, water was slowly added at a rate just sufficient to prevent the green color of the sodium alpha methylnaphthalene compound from spread,- ing through the solution. When the sodium had completely .reacted, carbon dioxide then was passed through the solution to convert sodium hydroxide to carbonate which was then filtered out. The filtrate was treated by blowing nitro-. gen through it to remove dissolved carbondioxide and was then reacted with 6 grams of sodium, allowing the solution to become colored. After this reaction had continued for. about 12 hours, water was slowly added to the reaction mixture until the color was discharged. The 'solution then was treated with carbon dioxide and filtered as before. The solvent ether then was distilled off and the residue was distilled under vacuum. The distillation products consisted of 5 grams of a viscous-liquid which was found to have a molecular weight-of about 243 and 13 grams of a solid, resinous, non-volatile residue which had a molecular weight of about 401. The lower mblecular weight fraction apparently was the dimer ,of dihydro alpha-methylnaphthalene,

' carbons.

while the higher molecular weight product appeared to be the trimer, containing a small amount of the dimer.

Example 9 The procedure of Example 8 was repeated, using beta-methylnaphthalene in place of alpha- .methylnaphthalene. In this case, the distillation product consistedof 11 grams of viscous liquid and'lgrams ofsolid resin having amolecular weight of about 411.

ltaxmtple 10 Acenaphthene (144 grams) was reacted with 60 grams of sodium at room temperature under an atmosphere of nitrogen in 1200 cc. of dimethyl During the reaction, water was the green color throughout the solution was prevented but the green color on the surface of the sodium was-not prevented. Whenthe sodium had completely reacted, the solution was treated with carbon dioxide to convert sodium hydroxide to the bicarbonate and the solution was filtered. Afterv evaporating 01f the solvent from the filtrate, the remaining mixture was distilled in vacuum at a pressure of about two millimeters of mercury. A fraction distilling over at 96 to 101 C. (1606 grams) was obtained. 'This product had a molecular weight of 154 which corresponds closely to the molecular weight of dihydro acenaphthene.

Example 11 hours atroom temperature. At the end of this time, water was added to decolorize the solution, carbon dioxide was passed in to convert sodium hydroxide to the carbonate and the solution was filtered The solvent ether was removed by evaporation and the residual liquid was vacuum distilled. The residue of the vacuum distillation consisted of a resinous material having a molec-- ular weight of about 463. This molecular weight indicated that the resinous product was mainly the trimer of dihydro acenaphthene, contaminated with a small amount of the dimer. I

A variety of substances are suitable for use as hydrolyzing agents in practicing our invention. These hydrolyzing agents are those substances which'are capable of reacting with sodium to release hydrogen and form sodium compounds.

.These hydrolyzing agents react with the sodium compounds of naphthalene and naphthalene homologs to replace the sodium with hydrogen;

. for example, water or alcohol reacts with disodium naphthalene to form dihydronaphthalene and sodium hydroxide or sodium alcoholate respectively; Various types of chemicals having replaceable hydrogen atoms are suitable as hydrolyzing agents in our process; for example, organic hydroxy compounds, e. g. alcohols, amino compounds, those ketones which will react with alkali metals to liberate hydrogen, e. g. dialkyl ketones or alkyl aryl ketones, organic acids, inorganic acids and unsaturated aliphatic hydro-- More specifically, the following have been found to be suitable as hydrolyzing agents: water, methyl alcohol, ethyl" alcohol, tertiary butyl alcohol, aniline, acetic acid and acetylene.

When water is used as the hydro'lyzing agent in practicing our invention, we have found it viously, the sodium hydroxide may be converted.

into one of various other sodium salts which are insoluble in the reaction medium. Alternately,

the sodium hydroxide or other water-soluble hydrolysis by-product, e. g. sodium alcoholate, may

be removed by washing the reaction mixture with water.

In the appended claims the terms naphtha. lene homolog and dihydro naphthalene homolog" are meant to include naphthalene and dihydro naphthalene, respectively, together with of acenaphthene and naphthalene. homoiogs with :analkall metal addition compound of one of said hydrocarbons and hydrolyzing the reaction product.

2. A process for making a resinous polymer comprising reacting the dihydro derivative of a naphthalene homolog with a sodium addition compound of a naphthalene homolog at a. temperature not lower than about 20 C. and hydrolyzing the reaction product. 3 3. Aprocess for making a resinous polymer of dihydron-aphthaiene comprising reacting dihydronaphthalene with a sodium addition com-. I

- pound of a naphthalene homolog at a temperature not lower than about 20 C. and hydrolyz-- ing the reaction product. 4

4. A process for making a resinous. polymer of dihydronaphthalene comprising reacting dihydronaphthalene with sodium naphthalene at atemperature of 20 to 30? C. and hydroiyzing the reaction product. v

'5. A process for making a resinous polymer comprising reacting sodium with a hydrocarbon selected from the group consisting of acenaphthene and naphthalene homologs in a suitable solvent ether until a substantial amount of the 7 sodium addition compound of said hydrocarbon is formed thereafter continuing the reaction at a temperature above about 20 C. and simultaneously hydrolyzing the reaction product atsuch rate that a substantial quantity of sodium hydrocarbon addition compound is continuously present. Y

homolog in a suitable solvent ether until a substantial amount of the, sodium addition compound of the naphthalene homolog is formed thereafter continuing the reaction at a temperature above about 20. C. and simultaneously b drolyzing the reaction product at such rate that a substantial quantity of sodium hydrocarbon addition compound is continuously present.

7. A process for making a resinous polymer of dihydronaphthalene comprising reacting sodium with naphthalene in a suitable solvent ether until a substantial amount of sodium naphthalene is formed thereafter continuing the reaction at a temperature of 20 to 30 C. and simultaneously adding water to the reaction mixture at such rate that a substantial quantity of sodium naphthalene is' continuously present.

8. A process for making a resinous polymer of dihydronaphthalene comprising reacting sodium with naphthalene ina suitable solvent ether until a substantial amount of sodium naphthalene is formed thereafter continuing 'the reaction at a temperature above about 20 C. and simultaneousiy adding an alcohol to the reaction mixture at such rate that a substantial quantity of sodium naphthalene is continuously present.

9. A composition of matter comprlsing a. resinous polymeric derivative of a. 1.4 dihydronaphthalene homolog having a molecular weight of not less than about 400 which is soluble in hydrocarbons but is insoluble in water and alcohols. 10. As a new. composition of matter, a solid resinous polymer of 1,4 dihydronaphthalene having a molecular weight greater than 400 and a melting point of about C. and which is soluble in hydrocarbons but is insoluble-in water and alcohols.

11. As a new composition of matter, a solid,

substantially colorless, transparent, slightly fiu- 

